Fungicidal composition



United States Patent FUNGICIDAL COMPOSITION No Drawing. ApplicationOctober 29, 1953,

Serial No. 389,146

26 Claims. (Cl. 260-102) This invention relates to novel metal rosinammonium phenoxide complex-metal carboxylic acid soap reaction products,and to fungicidal and insecticidal compositions containing the same.

In accordance with the present invention, it has been found that themetal rosin ammonium phenoxide complex-metal carboxylic acid soapcompounds produced by the reaction of a metal rosin ammonium phenoxidecomplex and a water insoluble metal soap of a carboxylic acid are novelcompounds which possess a high fungicidal activity on plants, textiles,paper, leather, wood, etc. that is, in general, greater than that of themetal rosin ammonium phenoxide complex or of the component materialsfrom which the phenoxide complex and the reaction products of thepresent invention are prepared. Additionally, the novel reactionproducts of the present invention are not phytotoxic or exhibitsubstantially no phytotoxicity and hence are particularly suitable forincorporation in compositions designed for use as fungicidal plantsprays, or in other fungicidal and insecticidal compositions designedfor the treatment of plant life. The novel reaction products of thepresent invention may be incorporated in varnishes, sealers, lacquers,paints, and the like, or in resins, waxes, greases and the like, and theresulting products are thereby made fungus-resistant.

In general, the novel reaction products of the present invention areprepared by reacting a metal rosin ammonium phenoxide complex with awater insoluble soap of a carboxylic acid at an elevated temperature atleast sulficient to place the reactants into homogeneous solution. Themetal of the complex may be nickel, copper, cobalt, zinc, silver, iron,chromium, mercury or other metal capable of forming a complex withammona. It is preferred to carry out the reaction at a temperature inthe order of about 250 to 400 F. Lower temperatures may be used, but ata sacrifice of time. Higher temperatures, up to the lowest decompositiontemperature of the reactants, may be used, if desired.

The proportions of the reactants may be varied Widely, as desired. Thus,stoichiometrical proportions or an excess of one reactant with respectto the other may be used.

The metal rosin ammonium phenoxide complex may be introduced as suchinto the reaction with the water insoluble soap or it may be formed insitu in the reaction mix. The in situ reaction is preferred. in the insitu reaction the rosin ammonium phenoxide may be preformed or it, too,may be formed in situ. The in situ formation of the phenoxide ispreferred. Thus, in the preferred procedure, the double salts of thepresent invention are formed by the reaction of a water insoluble soap,a rosin amine, a phenol and a Water soluble salt of a metal capable offorming a complex with ammonia.

The rosin ammonium phenoxide which may be used as a reactant inaccordance with the present invention may be made by reacting a rosinamine With a simple or substituted phenol as described in Patent No.2,513,429, granted July 4, 1950. The metal rosin ammonium phen-2,772,263 Patented Nov. 27, 1956 oxide complex which may be used as areactant in accordance with the present invention may be made byreacting a rosin ammonium phenoxide with a water soluble salt of a metal(nickel, cobalt, iron, aluminum, copper, zinc, mercury, silver, etc.)capable of forming a complex with ammonia. Examples of these solublesalts are copper acetate, zinc acetate, the acetates of the other namedmetals, and the formats, chloracetate, bromoacetate, chloride, sulfate,borate, carbonate, thiocyanate, etc., salts of metals capable of formingcomplexes with ammonia.

Examples of the rosin amines which may be used to form the phenoxidereactant of the present invention include the rosin amines made fromwood or gum rosin or various modified wood or gum rosins, such asdehydrogenated (disproportionated) rosin, hydrogenated rosin, orpolymerized rosin. The rosin. amines may also be the amines derived fromthe pure rosin acids in which abietyl amine is the amine derived fromabietic acid, dehydroabietyl amine is the amine derived fromdehydroabietic acid, dihydroabietyl amine is the amine derived fromdihydroabietic acid, and tetrahydroabietyl amine is the amine derivedfrom tetrahydroabietic acid. They may be the secondary tertiary rosinamines in which the hydrogens attached to the nitrogen are replaced bylower alkyl and alkylol groups, such as methyl dehydroabietyl amine,ethyl dehydroabietyl amine, dimethyl dehydroabietyl amine, diethyldehydroabietyl amine, isopropyl dehydroabietyl amine, butyldehydroabietyl amine, hydroxymethyl dehydroabietyl amine, hydroxyethyldehydroabietyl amine, and di(hydroxyethyl) dehydroabietyl amine. Similarsecondary and tertiary rosin amines having the nucleus of abietic acid,dihydroabietic acid, tetrahydroabietic acid, and polymerized abieticacid may also be used, as may also the other amines referred to in theaforesaid patent.

Examples of phenols which may be used to form the phenoxide reactant ofthe present invention are phenol, ortho amyl phenol, octyl phenol, nonylphenol, ortho, meta and para cresol, para chloro meta cresol and otherchlorinated cresols, tertiary butyl meta cresol, resorcinol, pyrogallol,xylenol, para tolyl phenol, xylyl phenol, methyl phenol, cumyl phenol,beta nap hthol, chlorinated phenols such as monochlorophenol,dichlorophenol, trichlorophenol, tetrachlorophenol, pentachlorophenol,nitrated phenols such as mononitrophenol, dinitrophenol, trinitrophenol,and nitrocresols, and the like.

The water insoluble soaps of carboxylic acids which are used asreactants in accordance with the present invention are water-insolublesoaps of a metal or a mixture of metals and a soap-forming acid or amixture of such acids. Thus, the soaps may be soaps of calcium, barium,magnesium, mercury, lead, cadmium, silver, thallium, manganese, cobalt,nickel, iron, copper, tin, aluminum and the like. The preferred soapsare the copper, zinc and nickel soaps because the results obtained withthese soaps are superior to those obtainable with the other soapsreferred to herein.

The soap-forming acids used in forming the aforesaid Water-insolublemetal soaps include monocarboxy-lic acids having at least 6 carbon atomsin the carboxylic acid and being not otherwise substituted than with ahydrocarbon radical and the hydroxyl radical, such as caproic acid,caprylic acid, capric acid, lauric acid, myristic acid, palmistic acid,stearic acid, oleic acid, linoleic acid, linolenic acid, palmitoleicacid, melissic acid, hydroxystearic acid, ricinoleic acid, and the like,and mixtures thereof.

used in forming the metal soaps used in accordance with the presentinvention are the mixed higher fatty acids derived from animal orvegetable sources such as, for example, sardine and other fish oils,lard, coconut oil, sesame oil, soybean oil, tung oil, corn oil orpartially or completely hydrogenated derivatives of such oils, fattyacids derived from carnauba, spermaceti, beeswax, can delilla Wax andlike waxes, and carboxylic acids derived from petroleum or otherhydrocarbons. Other soapforming acids which may be used are naphthenicacid, tall oil fatty acids, and hydroaromatic acids such as abietic acidand the like.

The following examples are illustrative of the preferred method whichmay be used to form the metal rosin ammonium phenoxide complex-waterinsoluble metal carboxylic acid soap reaction products of the presentinvention. In the examples the term parts refers to parts by weight.

Example 1 70 pants of magnesium acetate were added with stirring to 100parts of Z-ethylhexoic acid at 'a temperature of 350 to 420. F. Theheating and agitation were continued until the acetic acid liberated bythe reaction was vaporized. The addition of 100 parts of nonyl phenoland 1.00 parts of dehydroabietyl amine caused the temperature to drop to260 F. At this point 55 parts of copper acetate were added and thetemperature was raised to 340 F., where it was maintained for 15minutes, whereupon a clear solution was obtained and heatingdiscontinued. When the temperature dropped to 175 F., 235 parts of xylolwere added. The resulting composition was liquid at room temperature.

The composition of Example 1 was tested to determine its fungicidalactivity by treating duck samples with a xylol solution containing 5% ofthe copper rosin ammonium phenoxide complex-magnesium soap double saltas follows:

Samples of oz. specification army duck were cut into 10" x 30" piecesand the pieces were washed in soap suds, rinsed and dried. The driedpieces were passed through the testing solution so that completepenetration was obtained. They were then passed through a wringer toremove the excess solution. Approximately 21 50% wet-pickup wasobtained. The treated fabric pieces were then dried for 24 hours toobtain complete solvent release.

The treated and dried pieces of duck were leached for 24 hours inrunning water and buried horizontally in a well composted soilconsisting of 50% black loam and 50% pre-rotted manure, one-half inchbelow the soil surface. The moisture content of the soil was maintainedat approximately 30-50%.

After 28 days incubation in the soil bed, the fabric pieces were removedand examined. There was no evidence of degradation found in the treatedfabric pieces after burial and they had retained their original handcharacteristics. A control 10 x 30" sample of the aforesaid army du'ckcontaining no treatment was buried at the same time as the treatedpieces and under the same conditions. The control was completelydestroyed, being in the form of small deteriorated pieces at theconclusion of the 28 day test period.

Prior to impregnating the piece of duck with the solution of Example 1,it and the untreated piece of duck were tested for tensile strengths ona 500 lb. vertical Scott tester. Each had a tensile strength of 296 lbs.After the 28 day burial period the treated duck and the control piecewere removed from the soil, washed thoroughly in warm water to removeall soil particles and airdried at room temperature. Tensile strength onthe treated piece was then taken on the same Scott tester. It had atensile strength of 298 lbs. The control piece was removed from the soilin small deteriorated pieces which had lost their fabric strength andhence were not tested. Each of these small pieces was badly stained. Incontrast the treated piece was substantially free from stain.

Example 2 Example 1 was repeated except that a corresponding amount ofzinc oleate was used in lieu of the magnesium Z-ethylhexoate. A testsolution and fabric pieces were made up and tested against an untreatedfabric control piece, as described. The treated pieces showed no sign ofdegradation and no loss of hand, whereas the control piece hadcompletely deteriorated.

Example 4 Example 1 was repeated except that parts of dihydroabietylamine were used in lieu of the dehydroabietyl amine. A test solution andfabric pieces were made up and tested against an untreated fabriccontrol piece, as described. The treated pieces showed no sign ofdegradation and no loss of hand, Whereas the con trol piece hadcompletely deteriorated.

Example 5 Example 1 was repeated except that 100 parts of rosin aminemade from wood rosin were used in lieu of the dehydroabietyl amine. Atest solution and fabric pieces were made up and tested against anuntreated fabric control piece, as described. The treated pieces showedno sign of degradation and no loss of hand, whereas the control piecehad completely deteriorated.

Example 6 Example 1 was repeated except that a corresponding amount ofnickel 2-ethylhexoate was used in lieu of the soap of Example 1. A testsolution and fabric pieces were made up and tested against an untreatedfabric control piece, as described. The treated pieces showed no sign ofdegradation and no loss of hand, whereas the control piece hadcompletely deteriorated.

Example 7 Example 1 was repeated except that 100 parts of beta naphtholwere used in lieu of the phenol of Example 1. A test solution and fabricpieces were made up and tested against an untreated fabric controlpiece, as described. The treated pieces showed no sign of degradationand no loss of hand, whereas the control piece had completelydeteriorated.

Example 8 Example 1 was repeated except that a corresponding amount ofcopper oleate was used in lieu of the soap of Example 1. A test solutionand fabric pieces were made up and tested against an untreated fabriccontrol piece, as described. The treated pieces showed no sign ofdegradation and no loss, of hand, whereas the control piece hadcompletely deteriorated.

Examples 9, 10, 11 and 12 Example 1 was repeated except that 55 parts ofzinc acetate were used in lieu of the copper acetate. Example 1 wasrepeated except that 55 parts of mercury carbonate were used in lieu ofthe copper acetate. Example 1 was repeated except that 55 parts ofnickel chloracetate were used in lieu of the copper acetate. Example lwas repeated except that 55 parts of silver acetate were used in lieu ofthe copper acetate. Test solutions of these double salts and fabricpieces treated therewith were made up and tested against, an untreatedfabric control piece, as described. The treated pieces vernashowed nosign of degradation and no loss of hand, whereas the control piece hadcompletely deteriorated.

The reaction products of each of Examples 1 to 12, inclusive, in theform of the solutions described were individually applied to woodsamples 1 x 3" and leather squares 2" x 2" by soaking under vacuum for20 minutes and drying for 6 hours. The treated specimens and untreatedcontrol specimens of similar dimensions were placed on a sterilenutrient agar medium with a pH of 5.5, which was used for the substratumin the petri dishes in which the specimens were placed. Each treatedspecimen and a control specimen were placed in a single petri dish. Thespecimens in each of these dishes were sprayed with a spore suspensionof the following organisms and incubated at 30 C. for 14 days:Chaetomium globosum, Penicillium citrinum, Aspergillus niger,Aspergillus ferreus, Trichoderma virid, and Aspergillus flavus.

At the conclusion of this test period it was found that fungi weregrowing over the entire surface of the leather and wood controlspecimens and that no growth existed on the treated wood and leatherspecimens.

, The reaction products of the presentinvention can be used to treattextiles, paper, leather and the like by impregnating or coating thesematerials with a solution or dispersion of the reaction product in asuitable vehicle. Thus, the solutions described above may be used totreat these materials. These solutions may be compounded with resins,animal, vegetable and fish oils, plasticizers, flameproofing agents,driers, antioxidants and the like, in accordance with known techniques,to impart to the solutions desired properties. For example,characteristics such as spread and flow of these solutions may bemodified by the addition thereto of a fatty acid such, as lauric acid,oleic acid, linseed oil fatty acids, hempseed oil fatty acids and likefatty acids having from 8 to 20 carbon atoms in the chain, and of afatty acid glyceride, either raw or treated, such as raw or bodiedlinseed oil, China-wood oil,,castor oil, dehydrated castor oil, and thelike. Compatible natural and synthetic resins such as rosin,phenol-aldehyde resins, urea-aldehyde resins, vinyl resins and the like,or compatible cellulose derivatives such as nitrocellulose, cellulose,cellulose acetate, ethyl cellulose and the like may be incorporated inthe solutions invarying proportions to meet any desired needs.

Plasticizers such as glycol, glycerine, pentaerythritol, sorbitol,mannitol and other compatible plasticizers may be added to thesolutions. Suitable anti-oxidants which may be added to the solution arephenyl salicylate, tertiary butyl catechol and guaiacol, and suitabledriers are zinc naphthenate, lead naphthenate, cobalt naphthenate andzinc octoate.

If it is desired to impart water-proof properties to the solutions ofthe reaction products of the present invention, various waxes such asparaflin wax, bees wax, carnauba Wax, spermaceti wax, synthetic waxes,and the like, may be incorporated in the solutions in varyingproportions to meet the desired needs.

By a proper choice of the solvents for the reaction products of thepresent invention and of suitable modifying agents, the resulting liquidcompositions may be controlled as to consistency, drying time, flow,penetration, and the like.

Other solvents for the metal rosin ammonium phenoxide complex-metalcarboxylic acid soap double salt reaction product of the presentinvention are toluol, benzol, carbon tetrachloride, mineral spirits,naphtha, acetone, and the like.

Compositions containing reaction products of the present invention notonly inhibit the growth of fungus organisms but may also kill theactivity of all existing fungus growth on contact. Textiles, leather,wood, resins, etc., which have been treated with the reaction productsof the present invention are not attacked to any appreciable extent bysoil animal life and these treated materials resist the action ofbacteria and insects. The reaction products of the present inventionlend themselves for use as insecticides, in either dry or liquid form,and for preventing and combating diseases of plant life, both thosediseases which attack the parts of plants above ground and diseases suchas rot which attack underground parts of the plants. In dry form theactive ingredient is mixed with an inert diluent such as benrtonite,kieselguhr, talc, etc.

While the present invention has been described in connection withcertain specific examples of methods of making the reaction products, itis obvious that my invention is not to be construed as limited to thespecific materials disclosed in these examples or to the details of themethods set forth therein, since changes in materials, proportions andmethod details may be made without departing from the scope of myinvention as defined in the appended claims.

I claim:

1. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, a metal rosin ammoniumphenoxide complex, the metal of said complex being from a water-solublemetal salt capable of forming a complex with ammonia, and awater-insoluble monocarboxylic acid soap having at least 6 carbon atomsin the carboxylic acid, said carboxylic acid being not otherwisesubstituted than with a hydrocarbon radical and the hydroxyl radical.

2. The product produced by the method of claim 1.

3. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex and a Water-insoluble mono-carboxylic acid soap havingat least 6 carbon atoms in the carboxylic acid, said carboxylic acidbeing not otherwise substituted than with a hydrocarbon radical and thehydroxyl radical.

4. The product produced by the method of claim 3.

5. The method of forming a composition of matter comprising heating atan elevated temperature suflicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, zinc rosin ammoniumphenoxide complex and a water-insoluble mono-carboxylic acid soap havingat least 6 carbon atoms in the carboxylic acid, said carboxylic acidbeing not otherwise substituted than with a hydrocarbon radical and thehydroxyl radical.

6. The product produced by the method of claim 5.

7. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, nickel rosin ammoniumphenoxide complex and a water-insoluble mono-carboxylic acid soap havingat least 6 carbon atoms in the carboxylic acid, said carboxylic acidbeing not otherwise substituted than with a hydrocarbon radical and thehydroxyl radical.

8. The product produced by the method of claim 7.

9. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, cobalt rosin ammoniumphenoxide complex and a water-insoluble mono-carboxylic acid soap havingat least 6 carbon atoms in the carboxylic acid, said carboxylic acidbeing not otherwise 7 substituted than with a hydrocarbon radical andthe hydroxyl radical.

.10. The product produced by the method of claim 9.

11. The method of forming a composition of matter comprising heating atan elevated temperature suflicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, mercury rosin ammoniumphenoxide complex and a water insoluble carboxylic acid soap.

12. The product produced by the method of claim 11.

13. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition tem: perature of the reactants, copper rosin ammoniumphenoxide complex and magnesium 2-ethylhexoate.

14. The method or" forming a composition of matter comprisingheating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, a rosin ammonium phenoxide,a water soluble salt of a metal capable of forming a complex withammonia and a water-insoluble mono-carboxylic acid soap having at least6 carbon atoms in the carboxylic acid, said carboxylic acid being nototherwise substituted than with a hydrocarbon radical and the hydroxylradical.

15. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, copper rosin ammoniumphenoxide complex and a magnesium carboxylic acid soap.

16. The product produced by the method of claim .15.

.17. The method of forming a composition of matter comprising heating atan elevated temperature suflicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, zinc rosin ammoniumphenoxide complex and magnesium Z-ethylhexoate.

18. The method of forming a composition of matter comprising heating atan elevated temperature suificient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, zinc rosin ammoniumphenoxide complex and a magnesium carboxylic acid soap.

19. The product produced by the method of claim 18.

20. The method of forming a composition of matter comprising heating atan elevated temperature sufiicient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition tempera ture of the-reactants, a rosin ammonium phenoxide,a water soluble copper salt capable of forming a complex with ammoniaand a water-insoluble mono-carboxylic acid soap having at least 6 carbonatoms in the carboxylic acid, said carboxylic acid being nototherwisesubstituted than with a hydrocarbon radical and the hydroxylradical. 21. The method of forming a composition of matter comprisingheating at an elevated temperature suflicient to place the reactantsinto homogeneous solution, said temperaturebeing below the lowestdecomposition temperature of the reactants, a rosin ammonium phenoxide,a water soluble zinc salt capable of forming a complex with ammonia anda water-insoluble mono-carboxylic acidsoap having at least 6 carbonatoms in the carboxylic acid, said carboxylicacid being not otherwisesubstituted than with a hydrocarbon radical and the hydroxyl radical.22. The method of forming a composition of matter comprising heating atan elevated temperature sufficient to place the reactantsintohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, a rosin amine, a phenol, awater. soluble salt of a metal capable of forming a complex with ammoniaanda water-insoluble mono-carboxylic acid soap having at least 6 carbonatoms in the carboxylic acid, said carboxylic acid being not otherwisesubstituted than with a hydrocarbon radical and the hydroxyl radical.23.. The method of forming a composition of matter comprising heating-atan elevated temperature sufficient to .place the reactants intohomogeneous solution, said temperature being below the. lowestdecomposition. temperature of thereactants, dehydroabietyl amine,.nonylphenol, copper acetate and magnesium 2-ethylhexoate.

24. The method of forming a composition of matter comprising heating atan elevated temperature sufi'icient to place the reactants intohomogeneous solution, said temperature being below the lowestdecomposition temperature of the reactants, dehydroabietyl amine, nonylphenol, zinc acetate and magnesium 2-ethylhexoate.

25. The product produced by the method of claim 23. 26. The productproduced by the method of claim 24.

References Cited in the file of this patent UNITED STATES PATENTSSanders Dec. 30, 1952

1. THE METHOD OF FORMING A COMPOSITION OF MATTER COMPRISING HEATING ATAN ELEVATED TEMPERATURE SUFFICIENT TO PLACE THE REACTANTS INTOHOMOGENEOUS SOLUTION, SAID TEMPERATURE BEING BELOW THE LOWESTDECOMPOSITION TEMPERATURE OF THE REACTANTS, A METAL ROSIN AMMONIUMPHENOXIDE COMPLEX, THE METAL OF SAID COMPLEX BEING FROM A WATER-SOLUBLEMETAL SALT CAPABLE OF FORMING A COMPLEX WITH AMMONIA, AND AWATER-INSOLUBLE MONO-CARBOXYLIC ACID SOAP HAVING AT LEAST 6 CARBON ATOMSIN THE CARBOXYLIC ACID, SAID CARBOXYLIC ACID BEING NOT OTHERWISESUBSTITUTED THAN WITH A HYDROCARBON RADICAL AND THE HYDROXYL RADICAL.